ELASTOMERE UND KUNSTSTOFFE

ELASTOMERS AND PLASTICS

Carbon black distribution · SSBR/NR

blends · Styrene content · Vinyl content
The morphology development during
the mixing process of carbon black
filled SSBR/NR compounds was investi-
gated as a function of the styrene and
vinyl content of the SSBR by means of
the online electrical conductance, the
dispersion index and the wetting
behavior of the polymer to carbon
black. The phase selective filler distribu-
tion was determined using a thermo-
gravimetric method. The infiltration
time shifts for single mixtures to lower
values with increasing styrene content
in the SSBR. No clear tendency was
seen for the influence of the vinyl
content. For the 50/50 blends, the
behavior in the mixing process and the
resulting phase specific carbon black
distribution is dominated by the natu-
ral rubber and the compatibility of both
rubbers.
Einfluß von Styrol- und Vinylge-
halt von SSBR auf die Dispersion
und phasenselektive Füllstoff-
verteilung von Ruß in SSBR/
NR-Blends
Rußverteilung · SSBR/NR-Blends ·
Styrolgehalt · Vinylgehalt
Der Einfluss des Styrol- und Vinylgehal-
tes auf die Morphologieentwicklung
von rußgefüllten SSBR/NR-Mischungen
wurde mittels online gemessenem
elektrischen Leitwert, der Bestimmung
des Dispersionsindex und des Benet-
zungsverhaltens untersucht. Weiterhin
wurde die phasenselektive Füllstoffver-
teilung mit einer thermogravimetri-
schen Methode bestimmt. In den 100 %
SSBR-Mischungen wurde der erwartete
Einfluss des Styrolgehaltes, aber keine
klare Tendenz für den Einfluß des
Vinylgehaltes gefunden. In den binären
50/50 SSBR/NR-Blends wird hingegen
sowohl die Morphologieentwicklung
als auch die phasenselektive Füllstoff-
verteilung durch den NR und die Kom-
patibilität des SSBR mit dem NR be-
stimmt.
Figures and Tables:
By a kind approval of the authors
Styrene and Vinyl Content of
Styrene Butadiene Rubber
Dispersion and Phase Specific Distribution of Carbon Black in
SSBR/NR Blends
The anionic solution polymerization of Materials
styrene and butadiene allows the prepa- Solution styrene butadiene rubber (SSBR)
ration of tailor made solution styrene prototypes were polymerized anionically
butadiene rubber (SSBR) with adjustable with different contents of styrene (Table 1)
glass temperature in a range between and vinyl (Table 2). The SSBR prototypes
-98 °C to + 20 °C by variation of the sty- were to about 25 % tin coupled. The Moon-
rene (0-70 %) and vinyl (8-75 %) content, ey viscosity of all prototypes was adjusted
respectively. Natural rubber (NR) is often to about 61 ± 3 MU to avoid effects caused
used as a second rubber component for by different viscosities of the rubber.
tire treads. The glass transition tempera- Sprintan SLR 4601-Schkopau (Styron Deut-
ture of NR is more or less fixed and de- schland GmbH) with a significantly lower
fines the corresponding tire performance Mooney viscosity of 45 MU was used as ref-
(wet grip, braking distance, rolling resist-
ance, fuel consumption). The use of rub- 1 Variation of styrene content
ber blends of NR with SSBR is a common Styrene, Vinyl, ML1+4,
SSBR TG, °C
method to adjust the performance of the % % MU
tire to a desired profile. Furthermore, the
S0/V67 0 67 -41 58
use of reinforcing fillers, such as carbon
S14/V61 14 61 -34 60
black or silica, is required to achieve tech-
nically relevant mechanical-physical S21/V61 21 61 -27 62
properties. The incorporation of the filler S30/V62 30 62 -17 62
in the rubber blends is a very important
step in the preparation of the tire tread
2 Variation of vinyl content
and the resulting phase specific distribu-
tion influences significantly the overall Styrene, Vinyl, ML1+4,
SSBR TG, °C
% % MU
performance of the tire tread compound.
S48/V10 48 10 -29 64
The impact of compounding conditions
and compounding ingredients on blend S49/V22 49 22 -20 63
phase morphology and filler distribution
S49/V30 49 30 -15.5 60
was extensively investigated with differ-
ent methods in the past [1-5]. Several S50/V33 50 33 -13 60
new techniques were developed in the
last years to investigate the mixing proc-
ess and filler distribution to achieve a
better understanding of the structure- Authors
property relationships [6-10]. Target of E. Hamann, Schkopau, S. Ilisch,
this investigation was to analyze the in- H. H. Le, H.-J. Radusch, Halle
fluence of styrene and vinyl content of
the SSBR on the mixing process and the Corresponding author:
Evemarie Hamann
phase specific distribution of the carbon
STYRON Deutschland GmbH
black (CB) filler using such new developed 06258 Schkopau
experimental methods. Tel.: +49 3461 497154
E-Mail: ehhamann@styron.com

KGK · März 2011 33

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 ELASTOMERE UND KUNSTSTOFFE
ELASTOMERS AND PLASTICS

erence. The composition of SLR 4601 is with

1 1 Online measured
21 % styrene and 62 % vinyl the same as of
electrical conduct-
the SSBR sample S21/ V61. ance G and disper-
The development of the CB dispersion and sion index DI ver-
the CB distribution was investigated in sus the mixing
50 phr CB (N220, Evonik) filled compounds time
of these SSBR’s, natural rubber SMR10 (WE-
BER & SCHAER GmbH&Co. KG) and 50/50
SSBR/NR blends.

Methods
The compounding was done in a 78 cm³
chamber (Haake Rheomix 610p) using a fill
factor of 0.7 starting with an initial chamber
wall temperature of 50 °C and a rotor speed
of 50 rpm. At the end of the mixing process,
the mass reached a temperature of about
100 °C. Masticated NR was used for all in- 2
vestigations of the blends. The mastication
was conducted in the internal mixer at an
initial temperature of 70 °C, 50 rpm and fill
factor 0.45. The process was stopped when
the initial torque of about 70 Nm (corre-
sponding to a Mooney viscosity ML1+4
(100 °C) of 96 MU, Mw of 827 kg/mol, Mn of
353 kg/mol and Mz of 1,500 kg/mol) has
reached 30 Nm which corresponds to a
Mooney viscosity ML1+4 (100 °C) of 70 MU,
Mw of 608 kg/mol, Mn of 275 kg/mol and 2 Development of the CB dispersion and the conductance of the single compounds with
Mz of 1,000 kg/mol. different styrene content

Online measured electrical

conductance (OMEC) 3
The laboratory internal mixer PolyLab Sys-
tem Rheocord 300p is equipped with a com-
bined temperature and electrical conduct-
ance sensor [6] which allows the measure-
ment of the electrical conductance G during
the mixing process directly in the com-
pound with the online mode. The chamber
wall acts as the second electrode. The sen-
sor extends in a certain length into the
chamber to realize a good contact to the
material and to guaranty a sufficient stabil- 3 Comparison of masticated and non masticated natural rubber
ity against the appearing shear forces. The
online measured conductance directly in
the chamber during the mixing process dis- process. The second local maximum is the of the conductivity as well as CB dispersion
plays an integral value over the whole characteristic mixing time indicating when and distribution are determined by a very
chamber. It depends on the statistical prob- the distribution and dispersion process of complex behavior of the bulk in the mixing
ability of the temporary destruction and carbon black is well developed. At the be- chamber. Four main processes can take
reformation of the carbon black network in ginning of the mixing process the sensor is place simultaneously in this stage:
a complicated, stochastically three-dimen- surrounded by free carbon black causing a - Wetting of the CB surface by rubber
sional flow. Regardless this fact, the con- short circuit indicating a very high conduct- chains;
ductance-time curves show a characteristic ance. With increasing mixing time the free - Infiltration of the rubber chains into the
shape for all mixtures investigated, like as carbon black is encapsulated, and a distinct voids of the CB agglomerates;
shown in Figure 1. decrease of the conductance is observed - Break-up of agglomerates and/or de-
The dependence of the online conductance (Figure 1, stage 1). After passing a minimal tachment of small aggregates from the
on time shows a characteristic curve with value, the conductance of the mixture in- periphery of the agglomerates (erosion
two maxima. The first one is due to the creases again and reaches a local maximum dispersion process);
short circuit caused by free CB and has no (stage 2). Simultaneously, the values of the - Distribution of fine particles through the
importance for the control of the mixing CB dispersion sharply increase. The changes rubber matrix.

34 KGK · März 2011

 Thanks to the infiltrated rubber layer the
4
hydrodynamic stress can be distributed
throughout the whole infiltrated region
and can act to break up the agglomerates
or to remove fragments from the surface
of the agglomerate in sizes up to the infil-
tration depth. The acting dispersion mech-
anism depends on the interaction be-
tween polymer and filler as well as the vis-
cosity and polarity of the rubber [11-12].
Thus, the values of CB dispersion increase
in this stage simultaneously with the infil-
4 Development of the CB dispersion and the electrical conductance of the single com-
pounds with different vinyl contents
tration process. In case of erosion mecha-
nism small aggregates detached can build
a “CB cloud” surrounding the agglomer-
5 5 Rubber layer L of ates. These cloud aggregates are not de-
NR, S0/V67 and tectable by the optical microscopy but
S50/V33 as a func- they enlarge the conductive area of the CB
tion of mixing agglomerates. According to the “onion
times model” proposed by Shiga and Furuta the
clouds surrounding different agglomer-
ates can touch each other and build a net-
work that leads to an increasing contribu-
tion of the conductivity [13]. Furthermore,
due to the shear force and the mass trans-
fer the fine particles are distributed in the
rubber matrix. If the network is destroyed,
a decreasing contribution of the online
conductance is resulting. Thus, the in-
crease of the conductance in the stage 2 of
Figure 1 results from the dominance of the
increasing contributions caused by the
rubber infiltration and CB dispersion proc-
6 esses in comparison to the contribution
caused by the CB distribution process. This
dominance decreases with the mixing
time, and when it approaches zero the
conductance reaches the maximum. The
mixing time corresponding to the local
maximum conductance is the criterion for
the completion of the infiltration process.
Beyond this maximum, in the stage 3
(Fig. 1), the CB dispersion rate reduces pro-
gressively and the small aggregates are in-
6 Development of the CB dispersion and the conductance of the SSBR/NR blends with tensively distributed. The pronounced de-
different styrene contents cay of conductance in stage 3 is mainly
caused by the better distribution process
of the small aggregates in the rubber ma-
7 trix. The probability, that the gap width
between conductive clusters is lower than
3 nm [14] or 15 to 100 Å [15], decreases.

Dispersion index
The analysis of the carbon black macro-dis-
persion was done by optical microscopy.
For the estimation of the dispersion index
(Eq. 1) one produces gloss cuts by cutting
thin, stretched samples by a razor blade at
room temperature. The surface of the
7 Development of the CB dispersion and the electrical conductance of the SSBR/NR samples is checked by optical microscopy.
blends with different vinyl contents
If the surface of the cut contents carbon

KGK · März 2011 35

 ELASTOMERE UND KUNSTSTOFFE
ELASTOMERS AND PLASTICS

black agglomerates, the light is scattered

8
and its area appears dark. With an image
analysis program one can calculate the
area of larger CB regions (A in eq. 1). A0 is
the area of the picture and  the filler vol-
ume content in the mixture.  Med considers
the filler volume in the aggregates, accord-
ing Medalia [16]. The dispersion degree is
assessed as the amount of the non-dis-
persed agglomerates with an average di-
ameter larger than 6 m. For this investiga-
tion a research microscope RM-DX (Leica,
Germany) was used.

1 n
n
∑ (A ⋅ φMed )
D = (1 − i ) ⋅ 100 % (1)
φ ⋅ A0
Analysis of the wetting behavior of the
polymer to filler
The analysis of the bonded rubber layer on
the filler was done by solubility investiga-
tions of raw mixtures (seven days in cy-
clohexane, toluene or acetone). The calcula-
tion of the rubber layer L was performed
according eq. 2.

m2 − m1 ⋅ cR
L= (2)
m2
The mass m1 is corresponding to the rub-
ber compound before extracting, and it is
the sum of the mass of the undissolvable
rubber part, the mass of the soluble rub-
ber part and of the filler. m2 is the mass of
the rubber-filler gel, which is the sum of
the undissolvable rubber part and the
mass of the filler. cR is the weight ratio of
filler in the single rubber mixture or binary
blends. This value is dimensionless and
lies between 0 and 1. For blends, the
method was combined with thermogravi-
metric analysis (TGA/DTGA) of the rubber-
filler gel.
Determination of the phase selective
filler distribution by
thermogravimetric analysis (TGA/
DTGA)
Small pieces of the raw mixtures (nearly 0.5
g) are stored for seven days at room tem-
perature in 100 ml cyclohexane. The solvent
was totally replaced after three days. The
carbon-rubber-gel was dried and investi-
gated in the TGA Mettler-Toledo for the
mass loss in dependence of the tempera-
ture applying a heating rate of 20 K/min
covered by nitrogene in the range from am-
bient temperature until 600 °C and by oxy-
gene from 600-800 °C.
The characterization of the local carbon
black distribution between the different
rubber domains was carried out by thermo-
8 Phase images of CB filled 50/50 SSBR/NR blends for variation of the styrene content
gravimetric investigations for determina-
tion of LB( SBR ) and LB(NR ) according [10].
LB( SBR /NR ) is the rubber part in the rubber
filler gel of the blend and is the sum of LB(NR )
and LB( SBR ) of each blend component accord-
ing to eq. 3 [9].
LB( SBR /NR ) ( t ) = LB( SBR ) ( t ) + LB(NR ) ( t )
The carbon black phase distribution in a rub-
ber blend was calculated according to eq. 4
and 5.
RB( SBR ) ( t ) LPNR LB( SBR ) ( t )
= ⋅
RB(NR ) ( t ) LPSBR LB(NR ) ( t )
RB = RB( SBR ) ( t ) + RB(NR ) ( t ) + RBf ( t )
RB( SBR ) and RB(NR ) are the carbon black
amounts in SBR and NR blend phases, re-
spectively.
Atomic Force Microscopy (AFM)
Morphological investigations were carried
out by an atomic force microscope Q-Scope
250 (Quesant), operated in intermittent
mode with a scan-head of 40 m. Samples
were produced by cutting in a cryo-chamber
CN 30 of a rotary microtom HM 360 (Mi-
crom) with a diamond knife at -100 °C.
Results
Single rubber compound: styrene
content
The results for the development of the elec-
trical conductance G and the dispersion in-
dex during the mixing process of the carbon
(3) black filled SSBR compounds are shown in
Figure 2. To estimate the progress of the dis-
persion index in dependence on the mixing
time, the mixing process was stopped at
different times and samples were analyzed
by optical microscopy as described above.
(4) The commercial rubber SLR 4601 was used
as reference for all samples.
The run of the electrical conductance and
(5) the dispersion versus the mixing time de-
pends clearly on the styrene content. The
specimen rubber without styrene (S0/V67)
shows the longest infiltration time and the
longest time to reach a dispersion index of
96 %. With increasing styrene content (S14/
V61: 14 %, S21/V61: 21 % and S30/V62:
30 %) the infiltration and the sharp rise of
the dispersion values starts in tendency at
shorter times. The expected influence of
the higher polarity of the styrene content in
SSBR was observed.
The comparison of the commercial SLR 4601
with the sample S21/V62 shows further-

36 KGK · März 2011


9 9 Phase selective
10
11
more the strong influence of the rubber vis-
cosity on the development of the carbon
black dispersion. The distribution of the
filler is significant faster in a mixture with
SSBR of the same composition but lower
viscosity. Increasing the styrene content
from 21 % to 30 % provides a similar fast
time to reach the final dispersion index like
a reduction of the Mooney viscosity of the
totypes with different vinyl contents. The
curves of the electrical conductance show
carbon black distri-
bution in 50/50 no differences for the different vinyl con-
SSBR/NR-blends tent of the rubber and also the develop-
versus the styrene ment of the dispersion index shows no clear
content of the tendency for the vinyl content of the SSBR.
SSBR phase All SSBR of this series infiltrate and disperse
the CB faster than the commercial SLR 4601
which is caused by the significant higher
styrene content of about 49 % versus 21 %
of SLR 4601, which is in consistency with
the results discussed before for the influ-
ence of the styrene content.
Single rubber compounds: wetting of CB
The wetting behavior of the single rubbers
was investigated as described above. The
comparison of the wetting behavior of NR
10 Phase selective and SSBR is represented on example of S0/
carbon black distri- V67 and S50/V33 in Figure 5. It is obvious
bution in 50/50 that the rubber-layer LNR of NR and LSBR of
SSBR/NR-blends SBR (S0/V67 and S50/V33) increase with dif-
versus the vinyl
ferent rates. LNR and LSBR (S0/V67 and S50/
content of the
V33) reach a level-off value after about
SSBR phase
5 min and 7 min as well as 10 min mixing,
respectively. The rubber-layer LNR of NR in-
creases very fast in comparison to SSBR.
That is related to the high mobility of the
linear and flexible NR molecules versus rigid
SSBR molecules containing sterically hin-
dered phenyl rings. The higher the content
of styrene, the slower the wetting speed of
SBR.
SSBR/NR compounds: styrene content
11 Phase selective For the blends, the behavior in the mixing
carbon black distri- process and the resulting phase specific car-
bution in 50/50
bon black distribution is much more compli-
SSBR/NR-blends
cated. It was expected, that higher styrene
versus the differ-
ence of solubility content in the SSBR causes a higher affinity
parameters of the to the CB surface, because of the increased
rubbers polarity. For single mixtures this was shown.
The infiltration time of the specimen line
1 shift in tendency to lower values with in-
creasing styrene content in the SSBR (Fig. 3).
This trend is possibly also to observe in the
blend with NR but only in a very low degree
(Fig. 6). The increase of the styrene content
from 21 to 30 % (S21/V61 versus S30/V62)
cannot cover the difference of the rubber
viscosities of 15 MU between sample S21/
V61 and the commercial sample SLR 4601
SSBR by 15 MU. The same effect is well anymore. The dispersion behavior in the
known also for other rubbers and used es- blend is dominated by the natural rubber.
pecially in case of mastication of NR (Fig. 3). With increasing styrene content of the SBR,
the difference of the solubility parameter of
Single rubber compounds: vinyl the rubbers increases. In the blend the de-
content velopment of the conductance is dominat-
Figure 4 shows the curves for the electrical ed by the compatibility of the both rubbers.
conductance and the dispersion index in S0/V67 has the highest compatibility to NR
dependence on the mixing time for the pro- and shows the strongest change of the de-
KGK · März 2011 37
 ELASTOMERE UND KUNSTSTOFFE
ELASTOMERS AND PLASTICS
velopment of the conductance from the
single compound to the blend. Obviously,
the morphology development during the
mixing process of the rubber blends is influ-
enced not only by the wetting behavior of
the rubber chains to the CB surface, but also
by the viscosity and compatibility of the
rubbers and their affinity to the CB. The
mixing behavior in the blend is dominated
by the natural rubber.
SSBR/NR compounds: vinyl content
Figure 7 shows the electrical conductance
and the development of the dispersion in-
dex in dependence on the mixing time for
the blends with NR. The sharp increase of
the dispersion index of the blends shifts in
tendency to shorter mixing times with in-
creasing vinyl content in the SSBR. All con-
ductance curves for the blends run lower
than that for both single mixtures.
Phase specific distribution of CB
The morphology and phase specific distribu-
tion was investigated by AFM (Fig. 8).
The pictures show differences between the
morphology of the samples, but because of
the small dimensions of the polymer phas-
es, which are in the same level like the di-
mensions of the aggregates, it is not clearly
to separate, which polymer phase encloses
which carbon black content.
A clearer differentiation is possible using
the TGA/DTGA method.
There is a strong influence of the styrene on
the phase specific localization of the carbon
black in the binary 50/50 SSBR/NR blends.
Increasing the styrene content results in an
increased CB content in the NR phase (Fig. 9).
No influence of the vinyl content on the
phase specific CB distribution was observed
within the series with varied vinyl content.
However, looking at all investigated sam-
ples and including the sample with the
highest styrene content S30/V62 from the
first series with variation of the styrene
38 KGK · März 2011
content, a certain trend is to observe. In-
creasing the vinyl content results in an in-
creased CB content within the SSBR phase
(Fig. 10), contrary to the influence of the sty-
rene content.
Styrene and vinyl content are both influenc-
ing the compatibility of the SSBR with NR,
but in opposite direction. The solubility pa-
rameters of the SSBR’s were calculated
from the composition according to Schuster
et al. [17]. In Figure 11, the phase specific
distribution of the CB is compared with the
difference of the solubility parameter of
SSBR and NR (DSP (SSBR-NR)). The main influ-
ence factor on the phase specific CB distri-
bution in the 50/50 SSBR/NR blends is the
compatibility between both rubbers.
Conclusions
The systematic analysis of the mixing proc-
ess by means of online measured electrical
conductance, wetting behavior, macro dis-
persion and phase selective carbon black
distribution allows a new view on the mor-
phology development during the mixing
process. The online conductance is a helpful
tool for analysis and control of the com-
pounding process of polymers with electri-
cal conductive filler. We found a corre-
sponding change in online conductance
with rubber infiltration and carbon black
dispersion and distribution. The dispersion
mechanisms depend on polymer-filler com-
bination and differ significantly between
use of single rubber and use of binary
blends. The analysis of the rubber-filler gel
in connection with TGA/DTGA allows a
deep insight into the kinetics of the mixing
process. Carbon black content in the SSBR
phase of the 50/50-NR/SSBR-blends de-
creases with increasing styrene content of
the SSBR and increases with increasing vinyl
content in the SSBR. The carbon black con-
tent in the SSBR phase increases with in-
creasing compatibility of the SSBR with the
NR.
Acknowledgements
The authors are grateful to Styron Deutsch-
land GmbH for granting permission to pub-
lish this work.
The authors
Dr.-Ing. Sybill Ilisch and Dr.-Ing. Hai Hong Le
are co-worker in the Polymer Technology
group of Prof. Dr.-Ing. habil. Hans-Joachim
Radusch in the Center of Engineering Sci-
ence of the Martin Luther University Halle-
Wittenberg.
Evemarie Hamann is senior research spe-
cialist in Styron Synthetic Rubber.
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